Process for the production of o.o-dialkylphosphoric or o.o-dialkylthionophosphoric acid esters of n-alkylol lactams



PROCESS FOR THE KYLPHOSPHORIC PRODUCTION" OF (LO-DIAL- OR' 0.0DIALKYLTHIONO- PHOSPHORIC Afill) ESTERS F N-ALKYLOL LAC TAMS HeinzPohlemann and Harald Schroeder, Ludwigshafen (Rhine),

Badische Herbert Adolphi, Limburgerhol; Pfalz, Germany,

and Heinrich assignors to Stummeyer, Mannheim,

Anilin- & Soda-Fabrik Aktiengesellschaft;

Ludwigshat en (Rhine); Germany N 0 Drawing. Application May 28; 195TSerial No. 662,003

Claims priority, application. Germanyliunefi, 1956 r This inventionrelates to 2 Claims. (Ci. 260-4393) a process for the production of newesters of O;O-dialkylphosphoric or 0.0-dialkylthioon phosphorusoxyhalide's,

mono or di-chlorides of alkoxypho-sphoric acids or the correspondingthionophosphorus compounds.

the phosphoric acid esters already prepared in large num- We have nowfound that new valuable esters of phosphoric acid or reacting an.0.0-dialkyL phosphoric or' acid monohalide .of the general formulainWhich R and R aliphatic saturated alkyl groups with l thionophosphoricacid are obtain-edby thionophosphoric represent identical or differentlower hydrocarbon radicals, in particular to 4C-atoms, X is oxygen orsulfur,

and Hal is a halogen atom with a N- alkylol-lactam of the generalformula wherein R is hydrogen, alkyl or trichloroalkyl advantageously besubstituted by halogen, especially The reaction eral structure:

wherein Y is the HO CH N (CHDM radicals,

one with l to 4 C-atoms. These radicals above mentioned significance.products correspond to the following genradical remaining aftersplittingoff" the hydrogen atom from the hydroxyl groupof the N alkylol-lactamand is the original halide.

radical contained in the phosphoric acid pyrrolidone (2), N

As QO-dialkylphosphoric acidomo-nohalidesthere come into question thechlorides, bromide and iodides of 0.0-

Suitable N-alkylol laetamsare for example lactams or l tam thio ac sofwhich the lactam ringcontains 4 to C atoms'and which are substituted atthe nitrogen atombyt aliphatic hyd'rocarbon-radi'cals with 1 to othergroups; for examp 'ephenyl chlorphenyl,

nitrophen yl, propenylor cyclohexyl groups.

Especially suitable alkylol radicals are for example methylol,dihydroxyethyl I and beta-trichl'or alpha-hydroxyethyl radicals.resentatives of the l -a'lkylol lactams serving materials there maybe Ascrepas initial specified for example N-methylol- N hydroxypropylpyrrolidone (2), N methylolpiperidone (2), N hydroxyethyl. piperidone(2),

oenantholactam, N ydroXyethyl-caprylic J lactam,N-methylol-phthalimidine,.i N methylol menthone isoxime, N (alphaydroxy- 1 caprolactarn, and also N (phenylreaction components,'1n' ananhydrous media .it being chloro-hydroca'rbons, and also ketones; suchas acetone tetrahydrofurane reaction. The use of solvents is recomm 1ywhen one or 12,8659]; Patented Dec. 23, 1958 hydroxyethyl pyrrolidone(2),

methyl ethylketone, and ethers, especial 1y cyclic ethers with oxygencombined in the ring, such as carbonates can also be used for tractunited with the non-aqueous layer.

' ring. The whole is 3 a this purpose. The afores id m terialseffectively remove hydrogen haide as it is formed from the sphere of thereaction. This removal of the liberated halogen acids may be referred toas base neutr ization of the halogen acids.

Although the reaction proceeds perceptibly even in the cold. it ispreferable to work at higher temperatures, for exam le between and 100C., especially between 30 and 70 C.

The new OO-dialkylphosphoric or thionophosphoric acid esters of.N-alkylol lactams are excellent agents for combating nests morespecifically insect pests, especially housefiies Muscn dome'stz'ca) andaphides.

The following examples will further illustrate this invention but theinvention is not restricted tothese eX- arnples. The parts specified inthe examples are parts by weight.

Example 1 395 parts of pyridine are added to a mixture of 575 parts ofN-methylol-oyrrolidone-(2) and 1,500 parts of benzene and into thismixture, while stirring vigorously at room temperature. there are slowlyintroduced 940 parts of 0.0-diethyl-thionophosphoric acid chloride.

The whole is then stirred for about 6 hours at 60 C. and then a lowed tocool to room temperature. The reaction mixture is introduced into 1,000parts of water, the aqueous mixed stirred well throughout and thenallowedtozstand. Two layers occur, which are separated. The aqueouslayer is extracted with benzene and the ex- The benzene solution iswashed with water, dried and the solvent disstilled oif. 431 parts ofdiethyl-thionoohosphoric acid ester of N-methvlol-pyrrolidone areobtained as a yellow non-distillable oil of the formula:

By working in the same way but replacing the 1,500 parts of benzenepresent during the reaction by 3,000 parts of chloroform, there areobtained (afterstirring the reaction mixture for 5 hours at 50 C. afterthe addition of the diethyl thionophosohoric acid chloride has beencompleted. and after working up in a corresponding manner) 1.190 parts(corresponding to 89% of the theoretical yield) of thediethyl-thionophosphoric acid ester of N-methy1olpyrrolidone as a redoil.

:Example. 2

330 parts of CHr-CHQC (am-o o-om-om-N are obtained as a yellow nondistillable oil.

If the reaction is carried out by allowing a mixture of 320 parts ofN-(beta-hydroxyethyl)-pyrrolidone-(2), 196 parts of-pyridine and 1,000parts of benzene to flow at room temperature while stirring into 467parts of 0.0-diethylthionophosph'oric acid chloride, and furtherstirring for 2 hours at C. after the end of the addition, there areobtained, after working up in the way described above, 480 parts of theproduct specified in the preceding paragraph.

Example 3 564 parts of 0.0-diethyl-thionophosphoric acid chloride areintroduced at room temperature while stirring vigorously into a mixturewhich consists of 429 parts of N-methylol-caprolactam and 237 parts ofanhydrous pyridine. The whole is then stirred for 10 hours at 30 C.,

the reaction mixture allowed to cool to room temperature and introducedinto 500 parts of water and 1,500 parts of benzene. After working up themixture, as described in Example 1. There are obtained, after distillingoff the solvent in vacuo, 430 parts of 0.0-diethyl-O-(azacycloheptanone-(Z)-yl-( 1) )-methyl thionophosphate as a yellowishnon-distillable oil.

Example 4 550 parts of 0.0-diethyl-thionophosphoric acid chloride areintroduced while stirring well at room temperature into a mixture of 500parts of N-methylol caprylic lactarn, 500 parts of benzene and 231 partsof anhydrous pyridine. To complete the reaction, the whole is stirredfor about 4 hours further at 50 C. It is allowed to cool, the reactionmixture is diluted with 1,000 parts of benzene and poured into 1,000parts of water. After good thorough mixing, it is allowed to settle andthe phases are separated. From the non-aqueous phase, 373 parts of0.0-diethyl-thionophosphoric acid ester of N-methylol caprylic lactamare obtained as a yellowish non-distillable oil.

If the reaction is carried out in the same way while using 1,750 partsof chloroform instead of 500 parts of benzene, there are obtained, afterworking up, 778 parts of 0.0-diethyl-thionophosohoric acid ester ofN-methylol caprylic lactam. The yield amounts to 82.4% of thetheoretical yield.

Example 5 326 parts of N-methylol-phthalimidine are stirred into partsof ch oroform and 158 parts of pyridine are added. Then 376 parts of0.0-diethyl-thionoohosohoric acid chloride are introduced and the wholestirred for 5 hours at 45 to 50 C. to complete the reaction. it isallowed to cool, the reaction mixture shaken several times with water.the chloroform solution dried and the solvent distilled off in vacuo.460 parts of an oil of the formula it has excellent insecticidal action.

Example 6 932 parts of 0.0-diethyl-thionophosphoric acid chloride areallowed to flow slowly at room temperature while stirring into 650 partsof N-methylol-thiopyrrolidone(2) which are dissolved in a mixture of 392parts of pyridine and 500 parts of benzene. After further stirring for 5hours at 50 C., the whole is cooled, 500 parts of benzene are added andthe reaction solution is washed with water. After drying, the solvent isremoved under reduced pressure. 1,180 parts of the new ester areobtained as a reda'eeooie brown undistillable' oil in crude form. Theyield of ester formula obtained, which has the C'gH5-O v S of thetheoretical yield. Example 7 amounts to 84% A solution of 260 parts ofN-methylol-piperidone-(2) in 159 parts of pyridine and 1,500 parts ofchloroform further 5 hours at 50 C. and scribed in Example 1. reducedpressure, 302 the theoretical yield) then Worked up as de- Afterremoving the solvent under parts (corresponding to 53.4% of of thecompound of the formula ii are obtained as a brown non-distillable oil.

Example 8 390 parts of N-(alpha-hydroxy-beta-trichloroethyl)-caprolactam are dissolved in 1,000 parts of pyridine and reacted asdescribed in Example 6 with 282 parts of 0.0-diethyl-thionophosphoricacid chloride.

mg up, the reaction mixture has 1,500 parts of benzene ester of theformula are obtained as a dark brown oil.

Example 9 260 parts of N-methylol-pyrrolidone-(2) are dissolved in amixture of 1,500 parts of chloroform and 179 parts slowlyintroduced'into the mixture so temperature does not rise above 50 C.After the Whole has been added, the mixture is stirred. for another 4hours at 70 C., the reaction mixture washed with water, dried and thesolvent removed by distillation in vacuo. There is obtained as a residue320 parts of crude diethyl-phosphoric acid ester ofN-methylol-pyrrolidone-(2) as a yellow oil.

Example 10 433 parts of 0.0-diethyl-phosphoricacid chloride are slowlyintroduced at room temperature while E- -CH5 are obtained as an oilycrude product.

parts of 0.0-diethyl-phosphoric 433 parts of 0.0-diethyl-phosphoric acidchloride are slowly introduced at 10 to 15 C. while stirring into asolution of 430 parts of N-methylol caprylic lactam in 1,000 parts ofbenzene and 199 parts of pyridine. After new compound of the formulaCH2-CH2-CH2CHz c2H,-. o- 0OH2N fi cHroHroHz obtained as a residue in theform of a yellow-brown oil. Example 13 533 parts of diethyl-phosphoricacid acted as described in Example 12 with(beta-hydro-xyethyl)-pyrrolidone-(2) in a mixture of 500 parts ofbenzene and 245 parts of pyridine. After working up, 600 parts of thecompound of the formula chloride are re- E-OH2 are obtained. Thecompound is a yellow non-distillable oil.

Example 14 575 parts of N-methylol-pyrrolidone-(2) are dissolved in amixture of 3,000 parts of chloroform and 395 parts of pyridine. Into thesolution there are introduced while stirring, 800 parts of0.0-dimethyl-thionophosphoric acid chloride at such a rate that thetemperature does not rise above C. When all has been introduced, thewhole is stirred for another 5 hours at 50 C. The reaction mixture isallowed to cool and is Washed with tilled off under reduced pressure. Asa residue there are obtained 482 parts (corresponding to 40.3% of thetheoretical yield) of the new compound of the formula (TECH: as a palered non-distillable oil.

Example 15 i 400 parts of N4 thionophosphoric acid ester (56.6% of thetheoretical yield) are obtained as an orange-red oily crude productwhich cannot be distilled.

Example 16 (corresponding to 48% of the theoretical yield) are obtainedas a yellow, rather pure, undistillable oil.

Example 17 800 parts of 0.0-dirnethyl-thionophosphoric acid chloride arereacted, as described in Example 14, with a solution of 855 parts ofN-methylol caprylic. lactarn in 3,000 parts of chloroform and 505 partsof triethylamine. After working up, there are obtained 951 parts(corresponding to 64.4% of the theoretical yield) of the newthionophosphoric acid ester of the formula CHsO- CHrCHr-CHg-CH;

as a pale yellow undistillable oil.

Example 18 800 parts of 0.0-dimethyl-thionophosphoric acid chloride areadded as described in Example 14 to 645 parts ofN-(beta-hydroxyethyl)-pyrrolidone-(2) in 3,000 parts of chloroform and505 parts of triethylamine. After working up the reaction mixture, 803parts (correspond-v ing to 63.4% of the theoretical yield) of thecompound of the formula (iCH:

are obtained as a yellow non-distillable oil.

Example 19 800 parts of 0.0-dimethylthionophosphoric acid chloride areallowed to act, as described in Example 14, on a solution of 645 partsof N-methylol-piperidon'e-(2) in 3,000 parts of chloroform and 395 partsof pyridine. After working up, there are obtained 541 parts(corresponding to 42.7% of the theoretical yield) of the compound of theformula C H: l as an orange-red oil.

Example 20 l 575 parts of N-rnethylol-pyrrolidone-(2) are dissolved in amixture of 3,000 parts of chloroform and 395 parts of pyridine and then1,080 parts of 0.0-di-norma1-propylthiono-phosphoric acid chloride isadded to the solution at such a rate that the reaction temperature doesnot rise above 50 C. When all has been added, the whole is stirredfurther for 5 hours at 50 C. and the mixture then allowed to cool. Bythe usual working up, 1,130 parts (corresponding to 76.7% of thetheoretical yield of the new thionopho-sphoric acid ester are obtainedin the form of a red oil. The thionophosphoric acid ester Example 21 Asolution of 655 parts of N-methylol-thiopyrrolidone- (2) in 3,000 partsof chloroform and 395 parts of pyridine is reacted, as described inExample 14, with 1,080 parts of 0.0-di-normal-propyl-thionophosphoricacid chloride. By working up the reaction mixture in the usual mannerthere are obtained 1,370 parts of the compound of the formulaCH3-CH2CH2-O- S CHrCHa i CH;-CHrCH-O-- O--CH7-N The yield of the newcompound amounts to 86.7% of the theoretical yield.

Example 22 715 parts of N-methylol-caprolactam are dissolved in 3,000parts of chloroform and 395 parts of pyridine and then 1,080 parts of0.0-di-normal-propy1-thionophosphoric acid chloride are introduced intothe solution while stirring, at such a rate that the temperature of thereaction does notrise above 50 C. After the Whole amount of thethionophosphoric acid chloride has been introduced, the whole is stirredfor another 3 hours at about 50 C., the mixture allowed to cool andworked up as described in Example 14. After distilling oil the solventthere are obtained 1,272 parts (corresponding to 78.7% of thetheoretical yield) of the 0.0-di-normal-propylthionophosphoric acidester of N-methylol-caprolactam as a pale yellow non-distillable oil.

Example 23 855 parts of N-methylol-caprylic lactam, which are dissolvedin 3,000 parts of chloroform and 395 parts of pyridine, are reacted asdescribed in Example 22 with v 1,080 parts of0.0-di-normal-propyl-thionophosphoric acid chloride. After appropriateworking up, 1,371 parts (corresponding to 78.2% of the theoreticalyield) of the new compound are obtained as a pale yellow oil.

Example 24 "A solution of 645 parts of N-methylol-piperidone-(Z) Example25 A solution of 575 parts of N-methylol-pyrrolidone-(2) in 3,000 partsof chloroform and 395 parts of pyridine is reacted, as described inExample 14, with 1,080 parts of 0.0-di-isopropyl-thionophosphoric acidchloride. After working up, the new thionophosphoric acid ester isobtained in an amount of"- 1,181 parts as a reddish-'yellowoil. Theyield of the thionophosphoric' acid ester of the formula amounts to 80%of the theoretical yield.

Example 26 Example 27 1,220 parts of0.0-di-normal-butyl-thionophosphoric acid chloride are allowed to act,as described in Example 14, on a mixture of 575 parts ofN-methylol-pyrrolidone- (2), 3,000 parts of chloroform and 715 parts oftripropylamine. After working up, there are obtained 1,270 parts of thecompound of the formula 11C4He S CH2CH: OCH2N E CH2 the yield amounts to78.7% of the theoretical yield.

Example 28 1,220 parts of 0.0-di-normal-butyl-thionophosphoric acidchloride are allowed to flow so slowly while stirring into a solution of655 parts of N-rnethylol-thiopyrrolidone-(2) in 3,000 parts ofchloroform and 395 parts of pyridine that the reaction temperature doesnot exceed 50 After the introduction of the thionophosphoric acidchloride is ended, the reaction mixture is stirred for another 16 hoursat 35 C. and washed with Water. The washing waters are united andextracted with chloroform. The extracts are again added to the reactionmixture which has been washed with water. After drying this mixture, thechloroform is distilled off under reduced pressure. As a distillationresidue there are obtained 1,552 parts of0.0-di-normal-butyl-thionophosphoric acid ester of N-methylol-thiopyrrolidone-(2). The compound is a reddish-yellow oil. Theyield amounts to 91.4% of the theoretical yield.

Example 29 940 parts of 0.0-diethyl-thionophosphoric acid chloride areslowly added at 50 C. while stirring well to a mixture of 575 parts ofN-methylolpyrrolidone-(2), 690

parts of anhydrous potassium carbonate and 3,000 parts of anhydrousbenzene. When the addition is completed, the whole is stirred foranother 5 hours at the same temperature. The reaction solution is cooledto room temperature and filtered. The residue is extracted with benzeneand the extracts united with the filtrate. The benzene solution iswashed with water. After drying, the solvent is distilled off underreduced pressure. The residue consizts of 602 parts of the esterobtained in Example 1. The ester is a practically colorless oil. The

yield amounts to 45% of the theoretical yield.

Example 30' 940 parts of 0.0-diethyl-thionophosphoric acid chlo ride areslowly added at C. while stirring well to a mixture of 855 parts ofN-methylol-caprylic lactam, 530 parts of anhydrous sodium carbonate and3,000 parts of anhydrous benzene. When the addition is completed, thewhole is stirred for another 5 hours at the same temperature. Thereaction mixture cooled to room. temperature is filtered. The residue isextracted with benzene and the extracts/united with thefiltrate. Thebenzene solution is washed with water. After drying, the solvent isdistilled off .under reduced pressure. The residue consists of 1,410parts of the ester obtained in Example 4. The ester is a.,practicallycolorless oil. The yield amounts to 87.3% of the theoretical yield.

What we claim is:

1. A compound of the general formula wherein R and R are lower'alkylgroups of 1-4 C-atoms, X is selected from the group consisting ofoxygenand group, with the further proviso that said last-mentioned alkyl groupand said trichloromethyl group occur as R only once, it is an integer of1 through 4 and m is an integer of 3 through 7.

2. A process for the production of QO-dialkylp'hosphoric and-thionophosphoric acid esters of N-alkylollactams which comprisesintimately admixing an 0.0-dialkylphosphoric acidmonohalide of thegeneral formula in which R and R are lower alkyl groups of 14 C-atoms, Xis selected from the group consisting of oxygen and sulfur, and Hal is ahalogen with a N-alkylol-lactam of the general formula in which R is amember selected from the group consisting of hydrogen, an alkyl group of1-4 C-atoms, and a trichloromethyl group, with the further proviso thatsaid last-mentioned alkyl and -thionophosphoric acid esters byintermixing of an 0.0-dialkylphosphoric acid monohalide of the generalformula RO Hal in which R and R are allcyl groups of 1-4 C-atoms, X isselected from the group consisting of oxygen and sulfur and Hal is ahalogen atom in an anhydrous organic solvent media at a temperature ofto 100 C. with a N-alkylol-lactam of the general formula wherein R isselected from the group consisting of hydrogen, an alkyl group of 14C-atoms, and a trichloromethyl group, with the further proviso that saidlastmentioned alkyl group and said trichloromethyl group occur as R onlyonce, n and m are integers wherein n is 1 through 4 and m is Sthrough 7and X is as stated above, and during the ensuing reaction removinghydrogen halides as formed from the sphere of the reaction by baseneutralization of said acids.

4. The process as claimed in claim 2, wherein the reactants are used insubstantially stoichiometrically equivalent amounts.

5. The compound of the formula.

(i--CH2 6. The compound of the formula CHr-O- E'CH:

7. The compound of the formula CHa-O- s 12 8. The compound of theformula CzHs-O- s v t CHr-CH: CzH5-0- OC Hz-N 9. The compound of theformula CHr-CHg-C H3 CzHs-O- 0-CHa-N 10. The compound of the formulaCgHs-O- 8 CCHr-CHr-CHz 11. The compound of the formula No referencescited.

UNITED STATES PATENT OFFICE Certificate of Correction Patent No.2,865,912 December 23, 1958 Heinz Pohlemann et al.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

column 12, lines 4 to 7 claim 8, the right-hahd portion of the formulain each occurrence should read as shown elow instead of as in thepatent:

column 10, lines 50 to 52, second formula in claim 2, the left-handportion of the formula should read as follows instead of as in thepatent:

[SEAL] Attest: KARL H. AXLINE, ROBERT C. WATSON, Attestz'ng Qfiaer.Oommz'ssz'oner of Patents.

1. A COMPOUND OF THE GENERAL FORMULA
 9. THE COMPOUND OF THE FORMULA